Modulation of the spatial distribution of crystallizable emulsifiers in Pickering double emulsions

The unique role of the spatial distribution of crystallizable emulsifiers in regulating the structure and properties of double emulsions has been gradually recognized. Herein, we utilized crystallizable monoglycerides of different carbon chain length (GMS/GMP/GML) to "structuring" the intermediate oil phase of double emulsions during a two-stage emulsification process followed by a cooling treatment. A ternary eigenvector (I, M, E) based on the numerical processing of polarization images was invented to quantitatively characterize the distribution pattern of monoglycerides. Crystallization kinetics analysis and dissipative particle dynamic simulation were then employed to reveal the regulatory mechanism for the site-specific interface distribution behavior. Results suggested that the distribution pattern of monoglycerides could be pricesly tuned as the internal interface-, external interface- or oil-phase dominated one in double emulsions. The surface activity as well as crystallization rates of monoglycerides dominated the interfacial distribution kinetics, and the cooling gradient along the interface region further regulated their interfacial distribution potential. Specificly, shorter crystallization time (t_1/2) made GMP molecules rapidly solidified in oil phase, leading to the oil phase domninate crystallization (0, M, 0), whereas, slow crystallization rate rendered GML and GMS with sufficient time to diffuse to the interface, thus forming interfacial crystals ((I, 0, 0) and (0, 0, E)). The sensitivity of GML to cooling gradient along the interface region led to its preferential external interface distribution under cooling treatment. The presented study explored novel strategies that can be used in characterizing and manipulating the distribution pattern of crystallizable emulsifiers in multi-interface emulsion systems.